Photographic gelatin layer containing a di-(polyalkylene glycoxy) alkane



Patented Apr. 29, 194i j 2,240,472 UNITED sures PATENT OFFICE PHOTOGRAPHIC GELATIN LAYER CONTAIN- ING A DI-'(POLYALKYLENE v GLYCOXY) Donald R. Swan, Rochester, N.'Y., assignor to Eastman Kodak Company, Rochester, N. Y., a corporation ofNew Jersey No Drawing. Application March '19, 1940, Serial No. 324,804

6 Claims.

This invention relates to photographic lightsensitive materials, such as sensitized film, plates,

and paper, comprising layers in which sensitive a silver salts are suspended or dispersed in gelatin photographic materials. Y

My invention perhaps finds its greatest usefulness in the manufacture of photographic film in which a sensitive gelatin emulsion layer is applied to the film base, set by chilling, and

then, without drying, is overcoated with a protective gelatin layer, the sensitive gelatin emulsion layer containing such a spreading agent. The general process of coating film base with a sensitive gelatin emulsion layer, setting by chill- 'ing, and overcoating with a protective gelatin 'unevenly. Moreover, if the emulsion, while still in a wet, chilled condition, is overcoated with a protectivegelatin coating, air bubbles form between the emulsion layer and the protective layer. Either of these defects, of course, greatly,

' has surface-active properties, and not only acts as a spreading agent for gelatin, but by some mechanism not clearly understood, it prevents the formation of air bubbles between the gelatin 'layers when a wet, chilled gelatin emulsion layer containing the proper concentration of saponin of their more constant and controlled properties. Because of its varying quality, some batches of no.cm.ammonium-con saponln may cause an increase in fog or a decreasegin sensitivity in the sensitive emulsion, and in some cases may produce llttle'or no improveand synthetic agents are to be preferred because CHr-CH:

CHr-Ca.

saponin be employed in the emulsion layer or in the protective overcoating or other layer.

Other surface-active .materials have been or other suitable vehicle, and optionally com- 5 tried in place of saponin, but many of them, prising other layers as well. More particularly,- while they may act to some extent as spreading I it relates to the use of certain'agents to facilitate agents for gelatin, have been found to be enthe spreading of gelatin or other hydrophilic tirely ineffectivefor preventing the formation colloid layers which are deposited from a preof air bubbles when a wet, chilled gelatin emuldominantly aqueous medium and used in such 10 sion containing them is overcoatecl with a warm elatin solution, and many of them are objection- .able from the standpoint of fogging or desensitizing' the emulsion. I

I have found a class of surface-active com- ,pounds which are not only excellent spreadin 1 agents for gelatin and other hydrophiiic colloid layers which are deposited from a predominantly aqueous medium and used in photographic films, plates, and paper but which, when incorporated in layers such as sensitive gelatin emulsions, are superior to saponin in the prevention of bubble formation when the wet, chilled. emulsion layer is overcoated with a warm gelatin solution or other hydrophilic colloid of the time which is deposited from a predominantly aqueous medium. These compounds are the dipolyalkylene glycoxy) alkanes in which the alkenyl radical is selected from the group consisting of the and phatic alkenyl radicals containing from 8 to 18 carbon atoms and the di-cyclohexenyl dialkyl methanes in which each alkyl radical contains less than 3 carbon atoms, each polyalkylene glycoxy :chain contains from 5 to 20 alkylene lycol radicals, and the alkylene radical is selected from the group consisting of ethylene and propylene.

The dl-(polyalkylene glycoxy) alkanes' in I which the alkenyl radical is an aliphatic .alkenyl radical of from 8 to 18- carbon atoms, e. g. di- (polyethylene glycoxy) decane,

HO-OHi-CHa.(0.0Hz-CH2) .0.(0112)10.0.(CHLCHLO):.CHLCH2.OH

may be prepared in a manner similar to that 'is overcoated with a warm gelatin solution. alcohols of from- 8 to 18 carbon atoms, e. g. However, saponin, being anaturally occurring decamethylene glycol.

material of vegetable origin, is of varying quality. The di-(polyalkylene glycoxy) alkanes in which the alkenyl radical is a di-cyclohexenyl maybe prepared as follows: Phenol is reacted Wallace A. Bea'tty. to give the compound dlphenylol dimethyl methane,

C CuH OII (or the corresponding diethyl or methyl ethyl compound). This compound is hydrogenated as described in British Patent 274,439, to give the corresponding dicyclohexylol dialkyl methane. This is then condensed with ethylene oxide or -propylene cxida-m a manner similar to that shown in British Patent 443,559. Such com= pounds are mentioned in French Patent 272,302.

Any of these (11- (polyalkylene glycoxy) alliance may be incorporated in the sensitive gelatin emulsion at any point in its manufacture such that they will be present during its coating, in the proportion of from 0.075 to 1 part of the compound per 100 parts by weight of Wet elmlll sion. This gives a content of the compound il..l5% to in the dried emulsion layer. These compounds have no detrimental efiect upon the photographic properties of the emulsion, hut, on the contrary, improve them. the property of the spreading agent which prevents the formation of air bubbles when a wet. chilled gelatin emulsion is overcoated with a gelatin solution, also tends to prevent the icrmation oi air bubbles, repellent spots, etc.,-on

the surface of a sensitive emulsion containing,

such a spreading agent, when that emulsion,

- predominantly aqueous, the remainder of the and pyridine.

coated on a film, plate, paper, etc, is immersed" in a developer.

coxyf alliance defined. may he used in any one or more or the colloid layersusecl to loaild up a" photographic sensitive element-upon'e lease elloh as him, glass, paper, etc., which layers consist gelatin or other hydrophilic colloid which is posited from a predominantly aqueous medlgirn;

i. e., a medium used as the solvent for such.

terials in which water predoates,-the remmn tier of the medium contributing to giveagocd dispersion or the colloid. iftwo superposed} cel leid layers are present, either, neither on of which may he photographlcally sensitive, the

spreading agent may lie-used in either layer or in hath layers; However, where a wet, chilledlicht sensitive gelatin or cimflar layer is w he cvercoated with a warm solution or emulsion of gelatin or similar material, the presence of the spreading agent in the Wet, chilled layer is essential ior preventing the formation of all huhhles between the layers. Examples of such bydrophilic colloids other than gelatin, which ar meiul as layers in photographic plates, paper, etc, are the water-soluble cellulose rile rivatives such as well hydrolyzed celluloeeacetateco medium being an organic solvent which contributes to the dispersibility oi the colloid; examples of such organic solvents for this purpose are acetone, ethyl alcohol, ethylene glycol, monoacetln What I claim as my invention and desire to be secured icy-Letters Patent of the United States is l. Photographic sensitive material comprising a layer of a hydrophiiic colloid. depositable from a predominantly aqueous -medium, said layer containing from 9.75% to 10% of a di-(polyalitylene glycony) .alttane in which the alirenyl radical is selected from the group consisting of the aliphatic alisenyl'radicals containing from 8 to is carbon atoms and the di-cyclohexenyl diallsyl methanes in which each alkyl radical contains less than 3 carbon atoms, each polyalkylene glyco xy chaincontains from 5 to 20 allrylene glycol radicals, andfthe alkylene radlcal is selected from the group consisting of ethylene and p opy en 2. Photographic sensitive material comprising a gelatin layer containing from 0.75% to 10% ct a-clt-(polyallrylene glycoxyl allsane in which the ailrenyl radical is selected from the r up consisting oi the aliphatic allgenyl radicals containlns'from d -to is cal-hon atoms and the di-cycloheiienyl diaiiryl methanes in which each .alhyl radical contains less than 3 carbon atoms, each 'polyellrylene gig/cosy chain contains from.;5 to 20 'allrylene glycol radicals; and the allrylene radical is selecteol from the grou consisting of ethylene ancl'fpropylene.

3 Photographic sensitive material comprising chase and two superposed gelatinhlayers, in which the gelatin layer nearer the hasecontains ellsleneinfwhichthealhenyl radical is selected from the group consisting of the aliphatic allzenyl radicals containing from 8 tolo carbon atoms and" the di-cyclohe'nenyl dializyl' methanes in which each allsyl .rsdical oontainsless than 3 car llon atoms, each pclyalmlfene glycosy chain cent. from 5 to zo almleneelycolradicals,

' h-Photographic sensitive material comprising ehasei-a photo-scnsitlye gelatin emulsion layer and aseljatin'overcoa inscnithe emill io lfiin (described in U. S. Patent No. 2,119,49lbf Solo) and cellulose esters of hydrom monooarlrrnrz rll c acids, such as lactic or glycollic, and salts ofcel lulose esters of phthalic (described in U. 5. Patent No. 2,127,573 of Sheppard and U. S. Patent No. coarser of dlcarboxylic acids, such as.

which the photo s'ensitive gelatin emuloibtl layer cont nt from 0.75%";tol0.% of a di-(polyalkylone glycoxy) allrane' inwhich the'alkenyl radical is selected from the group consisting .ofthe' all phatijc allrenyl-radiealscontaining from 8 to 18' carbon atoms and thediacyclohexenyl dialkyl methanes in whicheachaikyl radical contains less than 3-carbonatorns, each polyalkylene glycoxy chain contains from to 20 alkylene glycol v radicals,and the elk'ylene radical is selected from stand), as well as polyvinyl alcohol; 8nd hydra 'lyzed polyvinyl acetate (described in applications of Wesley G. Lowe, Serial Nos. '3l8,559'- e.nd

3l8,560, fl1ed February 12, 1940) and water-sob. uble polyvinyl acetals (described in an application of Charles R. Fordyce, Serial No. 221,584, filled July 27, 1938, Patent No. 2,211,323). when colloids other. than gelatin are used, it may be desirable to coat them at different temperatures.

the group consisting of ethylene and propylene.

5. 1 h ctographic sensitive material comprising a selatinlayer contalining from 0.15% to 10% of a di-(pciyethyleneglycoxy) decane.

6. Photographic sensitive material coinprising a gelatin layer containing from 0.75% to 10% 0f methyl methane;

a 'dzR-dl-Kpolyethylene glycoxy-cyclohexyl) di- DONALD a. swAN'. 

